CN101801888B - Mixture containing quaternary ammonium compound and its use - Google Patents

Mixture containing quaternary ammonium compound and its use Download PDF

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Publication number
CN101801888B
CN101801888B CN200880107728.7A CN200880107728A CN101801888B CN 101801888 B CN101801888 B CN 101801888B CN 200880107728 A CN200880107728 A CN 200880107728A CN 101801888 B CN101801888 B CN 101801888B
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mortar
water
ammonium compounds
organic ammonium
quaternary
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CN101801888A (en
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A·科勒尔
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Akzo Nobel NV
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Akzo Nobel NV
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/16Nitrogen-containing compounds
    • C08K5/17Amines; Quaternary ammonium compounds
    • C08K5/19Quaternary ammonium compounds
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B40/00Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/0028Aspects relating to the mixing step of the mortar preparation
    • C04B40/0039Premixtures of ingredients
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20Resistance against chemical, physical or biological attack
    • C04B2111/21Efflorescence resistance

Abstract

The present invention relates to the use of quaternary organic ammonium compounds for reducing efflorescence in building material compositions. In addition, a mixture containing at least one quaternary organic ammonium compound and at least one water-soluble organic polymer and, if appropriate, further additives is described. The mixture according to the invention can be produced by a) mixing at least one quaternary organic ammonium compound and at least one water-soluble organic polymer in water with one another and, if appropriate, subsequently drying the aqueous mixture obtained, or b) mixing at least one pulverulent quaternary organic ammonium compound and at least one pulverulent water-soluble organic polymer with one another, or c) applying at least one liquid and/or dissolved quaternary organic ammonium compound to at least one pulverulent water-soluble organic polymer, in particular by means of spraying, adsorption, mixing, fluidized-bed drying and/or granulation.

Description

Comprise mixture of quaternary ammonium compound and uses thereof
The present invention relates to the purposes of quaternary organic ammonium compounds in the weathering that reduces material of construction.In addition, the present invention relates to the mixture that comprises quaternary organic ammonium compounds, the method for preparing this mixture and favourable purposes thereof.
Especially concrete base building material as concrete, plaster and mortar in the situation that weathering be known.Those skilled in the art refer to the lip-deep settling that turns white with weathering, and this settling forms mainly due to the calcium hydroxide disengaging, and calcium hydroxide is by continuing reaction for calcium carbonate from airborne carbonic acid gas.In this process, can also contain other salt deposit.Although this weathering is worth without any remarkably influenced the physics of base material conventionally, especially the in the situation that of coloured or gray face, will it think very boring.
In order to address this problem, in WO 2001/72658A1, WO 2005/097699A1 and WO 2006/094528A1 and WO 2006/094809A1, some suggestions are proposed, correspondingly prepare mortar material by the concrete selection of inorganic adhesive component.Its result can reduce weathering really, but for formulator, sets exactly as required performance characteristic and greatly reduces as the possibility of the coagulating property of mortar to be prepared, storage period, open hour and/or shrinkage character by changing these components.
In another approach, mention additive, additive is joined in the solid material of construction of water-setting and should prevent or reduce weathering.Therefore, for example GB 1,088,485A mentions and the water dispersion of the mixture of the high boiling fraction of Yatall MA resin and Yatall MA (also part is mixed with pitch) can be sneaked in concrete or be applied to subsequently on surface.The method of preparing this dispersion is very complicated and therefore expensive, and the dark extremely black color of mixture has greatly limited its range of application in the method simultaneously.In DE 33 21027A1, describe a kind of method, the reduction of weathering and the minimizing that water absorbs wherein especially also should occur.In the method separately or mixedly use the low molecule terpenes of terpene polymer, particularly liquid with other terpene hydrocarbon, the amount by it with 0.1-10 % by weight joins in the material of construction of cement.Adding with emulsification form or by the terpenes of spraying liquid or dissolving of compound based on terpenes carried out, and this makes the especially use in dry mortar become impossible.In addition; EP 1 767 506A1 described in the solid material of construction of water-setting for reducing weathering can be in water the powder of redispersion; this powder is made up of at least one organic constituent and at least one water-soluble organic polymer protective colloid; wherein said organic constituent comprises at least one and has the compound of saturated wholly or in part cyclic group; there is fusing point and the about 100-10 of approximately-20 to 250 DEG C; 000 molecular weight, and form stable dispersion with described water-soluble organic polymer protective colloid in water.
GB 2,343,448A has described the concrete for the freeze-thaw resistance with improvement of wall, wherein also can add additive to control weathering to it.As such additive, mention calcium stearate, lipid acid and salt thereof, polyvinyl alcohol, water-based latex, silane, siloxanes and composition thereof.Described for the enough intensity of the concrete of wall in order to give, add a small amount of trimethyl-glycine.
US 2005/0106336A1 and WO 2005/014256A1 have described the matrix material that is suitable for preparing cement based plate, have wherein added the material with antimicrobial properties.As Antimicrobe compound, can use organic and inorganic reagent.Quaternary ammonium compound is preferred kind.Not mentioned weathering.
In application DE 26 36 271A that announce, the method for preparing lightweight mortar with the pearlstone that accounts for main volume share is described.For this reason, except perlite, also add calcium hydroxide or calcium oxide and the tensio-active agent of cement and about same amount.Tensio-active agent to be used is preferably anionic nature, but can be also positively charged ion or nonionic character.Not mentioned weathering.
Very different due to mortar and concrete Application Areas, these also have very different compositions.Should supplement, for example another kind of cement, it is different production types or different quality, can show very different weathering characteristics.Whether weather condition have in weathering tendency and also play an important role at applied material of construction.According to the multiple different compositions of concrete and mortar, become be apparent that in the time that formulator can be selected from the differing materials for reducing weathering highly beneficial, to select the most suitable product for special formulation in every kind of situation.
Therefore the problem itself occurring is to provide elimination or at least very large degree and reduces the solid material of construction of material of construction, particularly water-setting as the additive of cement-based mortars and concrete weathering.In addition, additive should exist by powder type, particularly for dry mortar preparaton, with the known disadvantage of avoiding liquid starting material as lack freeze-thaw resistance or in the situation that not adding toxicity biocides limited package stability, and the in the situation that of dry mortar preparaton dosing simply.In addition, be necessary that and can easily this additive be incorporated in the mortar matrix of mixing with water or treat to mix with water, and needn't consider special blending means.Described additive is should be very easily wetting, redispersible or dissolve in mortar mix, and in matrix, should have easily and uniformly and distribute.It is also important that before required weathering availability sharply reduces, do not obtain unfavorable or diverse mortar performance with additive, additive should be introduced in existing mortar preparaton and do not change its performance.In addition, should not rely on other mortar raw material and quantitatively give additive, this allows formulator to have very high handiness.In addition, importantly the raw material of dry mortar and preparation cost not because this additive changes or only change to slight extent.
Shockingly, by quaternary organic ammonium compounds can be solved to described challenge for reducing the weathering of material of construction.
In addition, theme of the present invention still comprises the mixture of at least one quaternary organic ammonium compounds and at least one water-soluble organic polymer and optional other additive.
Conventionally, be not attracted on organic surface in quaternary organic ammonium compounds, particularly not being attracted to polymer beads is useful as on the surface of latex or dispersion time, and therefore for example not before preparing this type of polymerisate by appropriate method as letex polymerization and/or during just added, but in the time that these stir and/or mix with water, it can not rely on water-soluble organic polymer and moves in material of construction, or moves on the material of construction of application.
According to the present invention, in material of construction, can use all quaternary organic ammonium compounds, condition is that the weathering of described material of construction is reduced to appropriate level by they, and do not cause any or only insignificant disadvantageous effect as the variation of the delay of hydrated cementitious time or mortar workability.
As quaternary organic ammonium compounds (it is also called QAC), for purposes of the present invention or mixture of the present invention, preferably use the assorted aromatic compound of alkyl ammonium compound, group with imine moiety, N-alkylation and/or the amphoteric substance of straight chain, side chain and/or ring-type.
Preferred alkyl ammonium compound is those of amine type, wherein can use one or use several quaternary organic ammonium compounds simultaneously.Conventionally, especially preferred is that at least one quaternary organic ammonium compounds is formula (1), (2) and/or (3):
(N +R 1R 2R 3R 4)A - (1)
(N +R 1R 2R 3R 4) 2A 2- (2)
(N +R 1R 2R 3R 4) 3A 3- (3)
Wherein R 1, R 2, R 3and R 4represent to there is at least 1 C atom and organic group that can be identical or different, A -represent univalent anion, A 2-represent dianion, A 3-represent trivalent negatively charged ion.To be alkyl trimethyl ammonium salt prick ammonium salt (benzalkonium) as benzalkonium chloride, ester quat, ethoxylation quaternary organic ammonium compounds and the organobentonite based on three ethanol-methyl quaternary ammonium or di-alcohol-dimethyl quaternary ammonium compound conventionally as cetyl trimethylammonium bromide or ammonium chloride, dialkyl dimethyl ammonium salt, benzene to the Typical Representative of this class alkyl ammonium compound.
Preferred group with imine moiety is R 3=NR 1r 2 +a -type, wherein imidazolium compounds particularly preferably.The assorted aromatic compound of preferred N-alkylation is for example pyridine compounds.Preferred amphoteric substance is for example trimethyl-glycine or Yelkin TTS, and wherein especially preferred phosphatide is as phosphatidylcholine or sphingolipid choline (sphingocholine).
Conventionally, as the organic group R of quaternary organic ammonium compounds 1, R 2, R 3and/or R 4in at least one there is saturated and/or undersaturated C 1-C 4when alkyl, particularly methyl, ethyl, propyl group, butyl, be preferred.Very especially preferably one or several methyl and/or ethyl.
Conventionally, as organic group R 1, R 2, R 3and/or R 4in at least one be the saturated and/or unsaturated C of at least one straight chain, side chain, ring-type and/or aromatics 6-C 50alkyl and/or assorted alkyl, preferably C 6-C 40alkyl and/or assorted alkyl, particularly C 8-C 30alkyl and/or assorted alkyl, very especially preferably C 8-C 24when alkyl and/or assorted alkyl, be favourable.
In the time there is independent negatively charged ion, quaternary ammonium compound exists usually used as quaternary ammonium salt.Especially, in order to obtain these quaternary ammonium salts, conventionally can use representational negatively charged ion.As univalent anion A -, fluorion, chlorion, bromide anion, iodide ion, hydroxide ion, methylsulfate, bicarbonate radical and/or dihydrogen phosphate are suitable especially, as dianion A 2-, sulfate radical, carbonate and/or hydrogen phosphate are suitable especially, as trivalent negatively charged ion A 3-, phosphate radical is suitable especially.
The limiting examples of quaternary organic ammonium compounds be alkyl trialkyl ammonium salts as alkyl triethyl ammonium salt and/or alkyl trimethyl ammonium salt, particularly dodecyl trimethyl ammonium salt, cetyltrimethyl ammonium salt, docosyl leptodactyline, hexyl leptodactyline, octyl group leptodactyline, decyl leptodactyline, lauryl leptodactyline, tetradecyl trimethylammonium ethyl ammonium salt, cetyltrimethyl ammonium salt, octadecyl leptodactyline, dodecyl triethyl ammonium salt, hexadecyl triethyl ammonium salt, docosyl triethyl ammonium salt, hexyl triethyl ammonium salt, octyl group triethyl ammonium salt, decyl triethyl ammonium salt, lauryl triethyl ammonium salt, tetradecyl triethyl ethyl ammonium salt, hexadecyl triethyl ammonium salt, octadecyl triethyl ammonium salt and methyl diethyl thereof, dimethyl ethyl and triethyl similar compound, dialkyl group dialkyl ammonium salt is as dialkyl dimethyl ammonium salt and dialkyl group diethyl ammonium salt, particularly two (dodecyl) dimethyl ammonium, two (hexadecyl) dimethyl ammonium, two (docosyl) dimethyl ammonium, dihexyl dimethyl ammonium, dioctyl dimethyl ammonium, didecyldimethyl ammonium salt, dilauryl dimethyl ammonium, two (tetradecyl) dimethyl ammonium, two (hexadecyl) dimethyl ammonium, two (octadecyl) dimethyl ammoniums and methylethyl thereof and diethyl similar compound, wherein also comprise that hybridization thing is as octyl group octadecyl methyl ethyl ammonium salt or lauryl decyl methylethyl ammonium salt, trialkyl methyl ammonium salt and trialkyl ethyl ammonium salt are as three (dodecyl) methyl ammonium salt, three (hexadecyl) methyl ammonium salt, three (docosyl) methyl ammonium salt, three hexyl methyl ammonium salts, tricaprylmethylammonium salt, three decyl methyl ammonium salts, three (lauryl) methyl ammonium salt, three (tetradecyl) methylethyl ammonium salt, three (hexadecyl) methyl ammonium salt, three (octadecyl) methyl ammonium salt and methylethyl thereof and diethyl similar compound, wherein also comprise that corresponding hybridization thing is as octyl group octadecyl tetradecyl methyl ammonium salt or lauryl decyl docosyl ethyl ammonium salt, benzyl trialkyl ammonium salts is as phenylmethane ammonium salt and alkyl dimethyl benzyl ammonium salt, particularly dodecyl dimethyl benzyl ammonium salt, hexadecyldimethyl benzyl ammonium benzyl ammonium salt, docosyl dimethyl benzyl ammonium salt, hexyl dimethyl benzyl ammonium salt, octyldimethyl benzyl ammonium salt, decyl dimethyl benzyl ammonium salt, lauryl dimethyl benzyl ammonium salt, tetradecyl dimethyl benzyl ammonium salt, hexadecyldimethyl benzyl ammonium benzyl ammonium salt, octadecyl dimethyl benzyl ammonium salt, alkyl dimethyl benzyl ammonium salt is as benzyl dimethyl tetradecyl ammonium salt, benzyl dimethyl hexadecyl ammonium salt, benzyl dimethyl octadecyl ammonium salt, benzyl methylethyl octadecyl ammonium salt, and/or Fixanol is as lauryl or cetyl pyridinium salt, and alkyl isoquinolinium salt, dialkyl group alkylbenzyldimethylasaltsum saltsum.In addition, also can use benzene rope ammonium salt (benzethonium), imidazolium compounds and/or imidazolidine derivatives.
As quaternary organic ammonium compounds, also can use ester quat.In the frequent situation that uses ester quat, having at least one ester functional group and at least one quaternary ammonium group is possible as the known substance of structural element, the particularly quaternized ester salt of the quaternized ester salt of quaternized ester salt, lipid acid and the di-alcohol alkylamine of lipid acid and trolamine and lipid acid and 1,2-dihydroxypropyl dialkylamine.These products are for example with trade mark with sell.Product vGH-70, N, two (the 2-palm acyloxy ethyl) Dimethyl Ammonium of N-and f-75, c-4046, l80 and aU-35 is the example of this class ester quat.
In addition, also can use betaine compound, wherein preferably use and there is former sub-portfolio R 3n +-CH 2-X-COO -the compound of synthetic and/or natural appearance, for example trimethyl-glycine (Me 3n +-CH 2-X-COO -) and carnitine (Me 3n +-CH 2-CHOH-CH 2-COO -) (Me represent methylidene) and/or alkylamidoalkyl CAB.
The alkyl of quaternary organic ammonium compounds also can be replaced as F or Cl as hydroxyl, amine, acid amides, imines, carbonyl, carboxyl, silane, siloxanes, ether, thioether, ester, nitrile, sulfonic acid, epoxy, carboxylic acid anhydride, carbonyl and/or halogen by functional group.The minority limiting examples of mentioning is alkyl dimethyl hydroxyethyl ammonium salt and/or alkylamide-ethyl trimethyl ammonium ether sulfate.
Saturated and/or unsaturated C 6-C 50the molecular weight of alkyl and/or assorted alkyl is generally 77 or higher, is preferably 100 or higher, is in particular 115 or higher.In addition, when its molecular weight is approximately 2,000 or lower, preferably approximately 1,000 or lower, especially approximately 700 or be favourable when lower.
The molecular weight of preferred quaternary organic ammonium compounds is generally approximately 5,000 or lower, is in particular approximately 2,000 or lower, is very especially preferably approximately 1,000 or lower.
Mixture of the present invention comprises at least one water-soluble organic polymer.Normally synthetic polymer and/or biological polymer are as polysaccharide for it, and it can be natural and/or synthetic preparation.Described water-soluble organic polymer also may optionally be synthesis modification.Conventionally, water-soluble organic polymer, if they are not dissolved, at room temperature for solid be preferably macromolecular compound.In the time using several water-soluble organic polymer, also can use the combination of the compound of one or more natural compoundss and one or more synthetic preparations.
Conventionally do not there is or only has weak ion characteristic according to water-soluble organic polymer of the present invention.But, normally useful in the time that described water-soluble organic polymer does not have or only has a small amount of carboxyl.
The polysaccharide preferably using and derivative thereof are that cold-water-soluble polysaccharide and polysaccharide are as ether of cellulose, starch ethers (amylose starch and/or amylopectin and/or its derivative), guar gum ether and/or dextrin.In addition, can use synthetic polysaccharide as negatively charged ion, nonionic or positively charged ion mixed polysaccharide, particularly xanthan gum or Wellan glue.Polysaccharide can but and nonessential use-case as carboxymethyl, propyloic, hydroxyethyl, hydroxypropyl, methyl, ethyl, propyl group, sulfate radical, phosphate radical and/or the modification of chain alkyl chemistry.Other natural stabilising system is that alginate, peptide and/or protein are as gelatin, casein and/or soybean protein.Very especially, be preferably dextrin, starch, starch ethers, casein, soybean protein, gelatin, hydroxy alkyl cellulose and/or alkyl-hydroxyalkylcelluloswith.
The water-soluble organic polymer of synthetic preparation can be made up of one or more protective colloids; for example one or more molecular weight are 2; 000-400; 000 polyvinylpyrrolidone and/or polyvinylacetal; all or part of saponification and/or amino, carboxylic acid group and/or alkyl-modified polyvinyl alcohol; its degree of hydrolysis is preferably about 70-100 % by mole, is in particular about 80-98 % by mole, in 4% aqueous solution viscosity is preferably 1-50mPas, be in particular about 3-40mPas (recording according to DIN 53015) at 20 DEG C, and melamino-formaldehyde sulphonate, naphthaldehyde sulphonate, the block copolymerization product of propylene oxide and oxyethane, styrene-maleic acid and/or vinyl ether-maleic acid copolymerized product.Polymer oligopolymer can be nonionic, negatively charged ion, positively charged ion and/or amphoteric emulsifier as alkylsulfonate, alkylaryl sulphonate, alkyl-sulphate, the vitriol of hydroxyl alkanol, alkyl and alkylaryl stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate, alpha-sulfonated fatty acid, the ester of the vitriol of many ethoxylations alkanol and alkylphenol and phosphoric acid salt and sulfo-succinic acid, season alkylammonium salt, season Wan Ji phosphonium salt, polyaddition products is as polyalkoxide, for example every mole of straight chain and/or side chain C 6-C 22the adducts of alkanol, alkylphenol, higher fatty acid, higher fatty acid amine, uncle and/or secondary senior alkylamines 5-50 moles of ethylene oxide and/or propylene oxide, wherein alkyl is always preferably straight chain and/or side chain C 6-C 22alkyl.Very especially, be preferably the polyvinyl alcohol of synthesizing stable system, particularly partly-hydrolysed optional modification, wherein can use one or more polyvinyl alcohol optional and a small amount of suitable emulsifier combination.Preferred particularly modification and/or unmodified polyvinyl alcohol and/or polyvinylpyrrolidone of synthesizing stable system, the degree of hydrolysis of described polyvinyl alcohol is 80-98 % by mole, during as 4% aqueous solution viscosity is 1-50mPas.
The effect that the weight ratio of quaternary organic ammonium compounds and water-soluble organic polymer depends primarily on material therefor and will reach.It can be approximately 99: 1-approximately 1: 99, is preferably approximately 90: 10-approximately 10: 90, is in particular approximately 75: 25-approximately 25: 75.
Mixture of the present invention is powder, particle, the aqueous solution or water dispersion.
As powder or particle, it is conventionally easy to redispersion or is dissolvable in water in water.The mean sizes of powder or granular particle is generally at least about 10 μ m or larger, is preferably approximately 30 μ m or larger, is in particular approximately 50 μ m or larger, but should be maximum 10mm or less conventionally, is preferably about 4mm or less, is in particular about 1mm or less.In addition, when powder according to the present invention or particle is easy to flow, block is stable and be useful when stable storing.In the time that mixture of the present invention is the aqueous solution or water dispersion, solids content is generally about 10-75 % by weight, is in particular about 25-65 % by weight.
Mixture of the present invention also can comprise other additive.The content of the additive of the summation based on quaternary organic ammonium compounds and water-soluble organic polymer is not subject to any physical constraints.Therefore for example surfactant may be considerably less, and in approximately 0.01 % by weight or larger, and especially approximately 0.1 % by weight or larger, preferably in approximately 1 % by weight or larger scope.On the other hand, also the additive of suitable vast scale can be mixed with mixture of the present invention, for example filler or based on water-insoluble film-forming polymer can be in water the dispersion powder of redispersion.Now, for 1 part of mixture of the present invention, can be added to how about 1,000 part, approximately 500 parts especially at the most, preferred other additive of approximately 100 parts at the most.But in the time that mixture of the present invention is the aqueous solution or water dispersion, the solids content based on 1 part of mixture of the present invention adds and is not more than approximately 100 parts, is not more than especially approximately 20 parts, may be normally favourable while being preferably not more than other additive of approximately 5 parts.
Character to other additive does not limit, as long as they do not participate in any undesirable reaction.They have vital role conventionally in the application of mixture of the present invention, but this is not essential.In the time that mixture of the present invention is powder, normally favourable in the time that additive is also powder type, but also can add fluid additive.Preferably this before dry or during carry out.Therefore for example also can add other water-soluble and/or water-insoluble organic polymer.
Preferred additive is the defoamer of Powdered and/or liquid, wetting agent, and alkyl, hydroxyalkyl and/or alkyl hydroxyalkyl polysaccharide are as ether of cellulose, starch ethers and/or guar gum ether, and wherein said alkyl and hydroxyalkyl are generally C 1-C 4group, synthetic polysaccharide is as negatively charged ion, nonionic or positively charged ion mixed polysaccharide, particularly xanthan gum or Wellan glue, cellulosic fibre, dispersion agent, rheology control additive, particularly superplasticizer, thickening material and/or casein, aquation control additive, particularly coagulation accelerator, curing catalyst and/or retardant, air entraining agent, polycarboxylate, polycarboxylate ether, polyacrylamide, the polyvinyl alcohol of complete and/or partly-hydrolysed and optional modification, polyvinylpyrrolidone, polyalkylene oxide and polyalkylene glycol, wherein said alkylidene group is generally C 2and/or C 3group, wherein block copolymerization product also counts, dispersion based on water-insoluble film-forming polymer and can be in water the dispersion powder of redispersion, for example, based on vinyl-acetic ester, ethane-acetic acid ethyenyl ester, ethane-acetic acid ethyenyl ester-branched paraffin carboxylic acid vinyl acetate, ethane-acetic acid ethyenyl ester-(methyl) acrylate, ethane-acetic acid ethyenyl ester-vinylchlorid, vinyl-acetic ester-branched paraffin carboxylic acid vinyl acetate, vinyl-acetic ester-branched paraffin carboxylic acid vinyl acetate-(methyl) acrylate, branched paraffin carboxylic acid's vinyl acetate-(methyl) acrylate, pure (methyl) acrylate, cinnamic acrylic ester and/or styrene butadiene, hydrophober is as silane, silicon ester, siloxanes, polysiloxane, lipid acid and/or fatty acid ester, thickening material, filler and/or gather materials as grit and/or the dust of quartzite matter and/or carbonate matter, for example quartz sand and/or Wingdale dust, carbonate, silicate, layered silicate, precipitated silica, light filler is as hollow glass microballoon, polymkeric substance is as polystyrene spheres, aluminosilicate, silicon oxide, aluminium-silicon oxide, calcium silicate hydrate, silicon-dioxide, pure aluminium silicate, Magnesium Silicate q-agent, hydrated aluminium silicate, Calucium Silicate powder aluminium, calcium silicate hydrate, aluminium iron silicate magnesium, calcium metasilicate and/or scoriae, and volcanic ash is as metakaolin and/or latent hydraulicity component.Very especially preferred additive is polymeric dispersions, dispersion powder, polysaccharide, superplasticizer and hydrophober, particularly silane, silicon ester, lipid acid and/or fatty acid ester.In addition, also can add other additive for reducing weathering.
As silane, silicon ester, polysiloxane and/or siloxanes, can use in principle all silicoorganic compound.But, when they exist with the boiling point of silicoorganic compound used not too lowly under normal pressure with liquid or solid form, be preferably approximately 100 DEG C or be favourable when higher, but and nonessential.Described silicoorganic compound can be soluble, insoluble or only partly soluble in water.Preferred silicoorganic compound are chemical formula (R ") Si (OR " ') particularly xo ythe mixture of alkylakoxysiloxanes, wherein 0 < x < 2, 0.5 < y < 1.5, preferably 1.0 < x < 2.0, 0.5 < y≤1.0, condition is (2y+x)=3, radicals R " can be identical or different, R " represent to have the straight chain of 1-18 C atom, side chain or cyclic alkyl, other radicals R " ' can be identical or different, R " ' represent hydrogen or there is the straight or branched alkyl of 1-4 C atom, preferably H, methyl, ethyl, propyl group.In addition, tetraalkoxysilane, alkyltrialkoxysilaneand, dialkyl dialkoxy silicane are preferred silicoorganic compound, wherein straight or branched C 1-C 20alkyl can be used as alkyl and exists, and alkoxyl group can be used as straight or branched C 1-C 10alkoxyl group exists, and wherein in rear a kind of situation, preferably uses methoxyl group, oxyethyl group and/or isopropoxy.In addition, also can use can copolymerization alkylidene group substitute alkyl as vinyl, allyl group and/or (methyl) acrylic acid groups.
The method of preparing mixture of the present invention is also theme of the present invention.First method a) in, at least one quaternary organic ammonium compounds and at least one water-soluble organic polymer are mixed with each other in water, optionally subsequently that gained aqueous mixture is dry.
In the time that gained aqueous mixture is dry, this, lyophilize as dry in sprayed with currently known methods conventionally, fluidised bed drying, drum dried and/or flash drying are carried out, wherein according to the common preferably spray drying of the performance of mixture and/or drum dried.Spraying for example can be undertaken by spraying wheel, single part or multi-part nozzle.If needed, still aqueous mixture described in dilutable water, to obtain the appropriate viscosity for spraying.Drying temperature there is no physical constraints.But particularly for security consideration, it should not exceed approximately 200 DEG C conventionally, especially approximately 175 DEG C.Enough effectively dry in order to obtain, preferred approximately 110 DEG C or higher conventionally, especially approximately 120 DEG C or higher temperature.
Another kind of method b) in, at least one Powdered quaternary organic ammonium compounds and at least one powdery, water-soluble organic polymer are mixed with each other, the mixing of wherein said powder is preferably carried out in powder blenders, wherein also can use other blending means.
Another method c) in, the quaternary organic ammonium compounds of at least one liquid and/or dissolving is applied to at least one powdery, water-soluble organic polymer as on powdery polyethylene alcohol, ether of cellulose and/or starch ethers.Suitable method is known to those skilled in the art, and especially comprises spraying, absorption, mixing, fluidised bed drying and/or granulation.
Also can add in the methods of the invention other additive, wherein add and can during step a), b) and/or c) and/or afterwards, carry out.Preferably the additive of liquid, dissolving or dispersion is joined in liquid, preferably Powdered additive is joined in powder or particle.
Can join in material of construction or be applied on material of construction using quaternary organic ammonium compounds as one-component or as mixture.As mixture, the inorganic carrier material that can use mixture of the present invention or contain at least one quaternary organic ammonium compounds.As solid support material, can use all known solid support materials, condition is that they are suitable for adsorbing organic compound.Preferred solid support material comprises anti-hard caking agent, hydrated magnesium silicate, and granular titanium oxide, pure clay, Fuller's earth, the aluminum oxide of activation, vermiculite is if wilkinite, pearlstone and phosphoric acid salt are as sodium phosphate.Particularly preferably BET surface-area is 50m at least 2/ g, is in particular at least 100m 2the silicic acid of/g.
When mixture of the present invention is while being Powdered, particularly when it is normally favourable during for dry mortar.But, in the time that mixture of the present invention exists with liquid state, be also favourable, therefore can directly process it, this is important at 2 components system and industrial treatment material of construction in as concrete situation especially.In addition, subsequently can be for example by spraying and/or roll-in using them as the aqueous solution, dispersion, mashed prod and/or paste be applied on the surface of material of construction.
Those skilled in the art refer in particular to mortar, concrete, plaster, coating system and building adhesive by material of construction.Described material of construction contains one or more tackiness agents conventionally.As the tackiness agent in meaning of the present invention, can use inorganic and/or non-inorganic adhesive.The reduction of weathering usually occurs in the material of construction of application.Refer to that by the material of construction of application the material of construction that mixes with water is in its final form and obtain minimum strength in the present invention.In mortar and concrete situation, in the time solidifying beginning to after date or according to Vicat storage period, situation is normally such, and wherein the two is characterised in that viscosity obviously rises, and this has stoped further processing.
Non-inorganic adhesive can be used as powder, exists as height and/or low viscosity liquid.Be preferably water-soluble and/or can be in water the polymkeric substance of redispersion as the film forming dispersion based on emulsion polymeric product and epoxy resin and/or redispersible dispersion powder.
It is Powdered that inorganic adhesive is generally, and made by least following component especially: a) a kind of water solidification adhesive, particularly cement, b) a kind of potential hydraulic binder, particularly acid blast furnace slag, volcanic ash and/or metakaolin, and/or c) a kind of on-hydraulic tackiness agent, particularly calcium hydroxide and/or calcium oxide reacting under the impact of empty G&W.
As water solidification adhesive cement, particularly for example according to EN 196CEM I, II, III, the Portland cement of IV and V, preferably α-and/or calcium sulfate and/or the high alumina cement of β-half hydration and/or anhydrous form.As potential hydraulic binder, can use volcanic ash as metakaolin, calcium metasilicate and/or volcanic cinder, volcanic tuff, trass, floating dust, blast furnace slag and/or silica dust, there is hydraulic reaction with calcium source in it together with calcium hydroxide and/or cement.Particularly lime, great majority are calcium hydroxide and/or calcium oxide form, can be used as the on-hydraulic tackiness agent reacting under the impact of empty G&W.The mixture of the particularly preferably material of construction based on pure Portland cement, or Portland cement, high alumina cement and calcium sulfate, so, can join the potential hydraulicity and/or on-hydraulic tackiness agent in two kinds of systems if now needed.
The example of (being also often called filler) of gathering materials is grit and/or the dust of quartzite matter and/or carbonate matter, for example quartz sand and/or Wingdale dust, carbonate, silicate, chalk, layered silicate and/or precipitated silica.In addition, can use light filler as hollow glass microballoon, polymkeric substance is as polystyrene spheres, aluminosilicate, silicon oxide, alumina silicon, calcium silicate hydrate, pure aluminium silicate, Magnesium Silicate q-agent, hydrated aluminium silicate, Calucium Silicate powder aluminium, calcium silicate hydrate, silicon-dioxide and/or aluminium iron silicate magnesium, and clay is as bentonite, now filler and/or light filler also can have natural or synthetic obtained color.
Mixture of the present invention is preferred for the solid material of water-setting, in concrete and dry mortar.Except mixture of the present invention, these dry mortar preparatons particularly comprise at least one inorganic adhesive and conventionally comprise other mortar component that can be used for described preparaton, for example filler is as grit, silicate and/or carbonate, organic binder bond is as dispersion powder and/or polyvinyl alcohol, rheology control additive is as glycan ether, casein, superplasticizer and/or thickening material, and defoamer and/or the additive of controlling aquation are as setting accelerator and/or retardant.
Mixture of the present invention uses usually used as powder or particle.Therefore can special standby easy and economic mode they are processed into corresponding dry mortar, dry plaster and/or for concrete as cement, the particularly intervention compound of modified cement.This makes good especially dosing become possibility, and therefore mixture is distributed very equably in material of construction neutralization in the fragment of brick of manufacturing subsequently, building element and in thus obtained structure.Can add these dry mixture original positions being mixed simply of specified amount under water, and subsequently it processed.
But, in the preparation of material of construction, also mixture of the present invention can be mixed as independent component.In the situation of this embodiment, normally favourable in the time that material of construction component is mixed or mediated with the water of aequum, wherein just in time before adding water, add water during and/or add afterwards described mixture.But, also can first mixing water be joined in mixture, and be joined by this way in dry material in mixing tank or wetting material.
The dry mortar preparaton that comprises at least one tackiness agent and at least one mixture of the present invention is also theme of the present invention, now described dry mortar preparaton can be mixed with to for example thermal insulating plaster, sealed compound, gypsum and/or Wingdale and/or cement plaster, repairing mortar, brick and tile grout, ceramic tile tackiness agent, glued board mortar, mortar for inorganic adhesive, cement priming paint, the reinforcement of concrete bonding coating, parquet floor tackiness agent based on cement, all be coated with and/or trowel is coated with compound.Can be out of doors and indoor use dry mortar preparaton of the present invention.In addition, can be used as concrete additive and/or the additive for concrete paint according to powder of the present invention and particle and undried mixture.
Other theme of the present invention is formed by the mortar or the concrete that contain at least one tackiness agent and at least one mixture of the present invention, wherein Steel Concrete, cellular concrete, gas concrete, foamed concrete, by concrete, mortar, plaster, the precast segment that joint sealer is made, the component parts of being made by lime-sandstone, clinker, brick, porous brick and tile and Dutch brick and tile, terra cotta, natural stone, fibrosis cement, floating screed, clay-ware, brick structure, buildings facade, roof, and buildings is as bridge, harbour, residential building, industrial building and office premises are as garage parking, station or school, and pre-constructed unit is particularly suitable as concrete as railroad sleeper or L-stone.
Except mixture of the present invention, dry mortar preparaton of the present invention, mortar and/or concrete are advantageously containing having an appointment 0.5-approximately 50 % by weight, the tackiness agent of about especially 1.0-approximately 30 % by weight ratios, about 30-99 % by weight, gathering materials of about especially 50-98 % by weight ratio, about 0-30 % by weight, especially approximately 20 % by weight ratios can be in water the film-forming polymer powder (often also referred to as dispersion powder) of redispersion, about 0-2.0 % by weight, the polysaccharide of especially approximately 1.0 % by weight ratios, and other component of about 0-25 % by weight is as calcium hydroxide and/or calcium oxide, wherein in the time using, the latter is preferably with approximately 10 % by weight at the most, the amount of special approximately 5 % by weight is at the most used, wherein said amount equal solids content based on described preparaton in each case.
Conventionally the consumption of quaternary organic ammonium compounds or the mixture that comprises quaternary organic ammonium compounds is selected, thereby made reduction the best of weathering.This refers to and with the naked eye no longer can be observed any weathering.But, because material of construction can, for example very different each other aspect composition, application bed thickness and/or climatope, be therefore favourable in the time that consumption mates with corresponding material of construction.Shockingly find purposes and mixture of the present invention for quaternary ammonium compound of the present invention, minimum is just enough to obviously reduce the weathering characteristic of material or it is eliminated completely.Preferably, consumption is at least about 0.0001 % by weight, especially at least about 0.001 % by weight, very especially preferably at least about 0.005 % by weight, and/or maximum approximately 5 % by weight, maximum especially 2 % by weight, very especially preferably maximum approximately 1 % by weight, based on material of construction, dry mortar preparaton, mortar and/or concrete solid body.
Be ready to use according to quaternary organic ammonium compounds and mixture of the present invention in application of the present invention and be highly susceptible to and material of construction, particularly with the material of construction phase miscible that contains the inorganic coagulating component stirring with water.In the time that quaternary organic ammonium compounds and/or mixture of the present invention exist with powder or particle form, they have extraordinary wettability conventionally.In addition, solvability and redispersible are very good respectively, and from contacting with water in several seconds, by gentle agitation, described mixture dissolves or redispersion completely in any case.In addition, conventionally only need minimum quaternary organic ammonium compounds, this is normally very favorable.
Explain the present invention with reference to following examples.
The preparation of powder
Embodiment 1: the preparation of powder 1
87.5g being purchased to calcium carbonate/magnesium (Dolomit DR80C) in mortar mill mixes completely with 12.5g benzalkonium chloride (Merck).Result is the homogeneous powder powder mixture that is easy to dosing.
Embodiment 2: the preparation of powder 2
In 500ml has the Glass Containers of propeller stirrer, 1,000rpm stir and room temperature under, be 88 % by mole and during as 4% solution to 292g saponification degree viscosity is to add 30g benzalkonium chloride (Merck) in 24% polyvinyl alcohol solution of 4mPas, and in described process, benzalkonium chloride dissolves completely.Gained solution with water is diluted to 500-1, the Brookfield viscosity of 000mPas (under 23 DEG C and 20rpm), in the situation that there is no other additive, be at 120 DEG C, to spray to be dried by routine to be dried into lurid powder soluble in water in temperature in subsequently, in described process, in spray tower, do not observe noteworthy fouling, and yield is in normal range.
Embodiment 3: the preparation of powder 3
90g is purchased to calcium carbonate/magnesium (Dolomit DR80C) to be mixed with 10g powder 2 (from embodiment 2).
B) use the application specific of cement-based material to test.
Embodiment 4:
Using 35.0 parts of Bai Bulante cement, 19.2 parts of quartz sands (0.08-0.2mm), 65,0.3 part of ether of cellulose of the 41.0 parts of calcium carbonate Durcal (viscosity during as 2% aqueous solution: 3,200mPas), 110 and 1.0 parts of building limes of 2.0 parts of pigment Bayferrox fully mix, and used as basic dry mortar formula.Add the following various amounts from table 1 to these different powder, described powder can be easy to be stirred to does not need other Special Mixed technique in mortar matrix.In every kind of situation, all use 60mm propeller type stirrer with 950rpm speed, described formula to be mixed 60 seconds with 32 parts of water (based on 100 parts of dry preparatons), the mixing water of amount shown in adding under wherein stirring.After 3 minutes digestion times, manual this mortar of simple agitation again, and it is applied on unglazed porcelain brick to (196mm × 50mm) size with 6mm thickness with trowel, wherein just in time use water saturation ceramic tile before.In every kind of situation, prepare two different samples, wherein apply described mortar by means of backing plate with the bed thickness of 2.0mm.
Then, in the environmental chamber that is cooled to 7 DEG C, directly sample is arranged in the container with the constant water that is heated to 20 DEG C.Thereby building described container makes sample be positioned at least 5cm and have the inclination of 45° angle of water surface top.Cover and the coated region not covered by sample, enter and pass sample thereby make water vapour pass solid support material.After the storage period of 7 days, optically with regard to weathering, (eyes and microscope) assessed in described surface.
Table 1: the application specific embodiment based on dyeing cement based trowel painting material that is 2.0mm for the bed thickness of weathering assessment.In all experiments, mortar workability is good, and consistency of mortar is suitable with reference example in every kind of situation.
Experiment numbers Basic components [weight part] Powder numbering Content of powder [weight part] QAC-content a)[% by weight] Weathering
1-a 98.5 N/A 0 0 Very obvious
1-b 98.5 1 0.4 0.05 Nothing
1-c 98.5 1 0.2 0.025 Nothing
1-d 98.5 b) 1 0.2 0.025 Nothing
1-e 100 c) 0.1 0.1 Nothing
1-f 100 d) d) 0.1 Nothing
A) QAC represents quaternary ammonium compound.
B) the ethane-acetic acid ethyenyl ester dispersion powder that adds in addition 3pbw to be purchased to 98.5 weight parts (pbw) basic components.
C) powder used is that (pure Yelkin TTS, from Central Soya EuropeanLecithins GmbH & Co KG for Centrolex FSB; Hamburg).
D) use the aqueous solution of palmityl trimethyl ammonium chloride (Dehyquart A CA, from Cognis) to replace powder.
Result clearly shows described sample, even, in the time that they contain very small amount of quaternary ammonium compound, has reduced so significantly weathering or even it has been eliminated completely, also can not observe even under the microscope.On the other hand, demonstrate very significantly weathering with reference to sample.
Embodiment 5:
Using the grit of the grit of the quartz sand of 28.0 parts of Bai Bulante cement, 25.0 parts of 0.1-0.3mm, 8.0 parts of 0.7-1.2mm, 35.0 parts of 1.5-2.2mm, the 0.05 part of ether of cellulose (viscosity during as 2% aqueous solution: 15,000mPas) He 2.0 parts of pigment Bayferrox 110 fully mix, and used as basic dry mortar formula.In every kind of situation, described formula is mixed with 17 parts of water (based on 100 parts of dry preparatons), and test in mode similar to Example 4.
Table 2: the application specific embodiment based on ornamental coloured plaster that is 2.2mm for the bed thickness of weathering assessment.In all experiments, mortar workability is good, and consistency of mortar is suitable with reference example in every kind of situation.
Experiment numbers Basic components [weight part] Powder numbering Content of powder [weight part] QAC-content a)[% by weight] Weathering
2-a 100 N/A 0 0 Very obvious
2-b 100 1 0.4 0.05 Nothing
2-c 100 2 0.16 0.05 Nothing
2-d 100 2 0.05 0.006 Nothing
2-e 100 3 1.6 0.05 Nothing
2-f 100 3 0.8 0.025 Nothing
2-g 100 3 0.4 0.012 Nothing
2-h 100 2 0.32 0.1 Nothing
A) in table 1
The quaternary ammonium compound that listed result shows is even very a small amount of (for example only 0.006 % by weight, based on solid body) has also caused in ornamental coloured plaster that very significantly weathering reduces, thus the variable color that does not have naked eyes to identify.In addition, other mortar performance does not change or complete insignificant change only occurs, for it is fresh mortar or in curdled appearance.

Claims (15)

1. quaternary organic ammonium compounds reduces the purposes of the weathering of material of construction in material of construction, wherein join in material of construction quaternary organic ammonium compounds as mixture, wherein said mixture comprises at least one quaternary organic ammonium compounds and at least one water-soluble organic polymer and optional other additive or the inorganic carrier material for containing at least one quaternary organic ammonium compounds.
2. according to the purposes of claim 1, it is characterized in that described mixture is powder, particle, the aqueous solution, dispersion, mashed prod and/or paste.
3. according to the purposes of claim 1 or 2, it is characterized in that described water-soluble organic polymer represents synthetic polymer.
4. according to the purposes of claim 3, it is characterized in that described synthetic polymer is modification and/or unmodified polyvinyl alcohol, polyvinylpyrrolidone, polycarboxylate ether and/or formaldehyde condensation products.
5. according to the purposes of claim 1 or 2, it is characterized in that described water-soluble organic polymer represents the biological polymer of natural and/or synthetic preparation, its optional synthesis modification.
6. according to the purposes of claim 5, it is characterized in that described biological polymer is starch, starch ethers, dextrin, ether of cellulose, casein and/or soy-protein.
7. according to the purposes of any one in claim 1,2,4 and 6, it is characterized in that at least one quaternary organic ammonium compounds has formula (1), (2) or (3):
(N +R 1R 2R 3R 4)A - (1)
(N +R 1R 2R 3R 4) 2A 2- (2)
(N +R 1R 2R 3R 4) 3A 3- (3)
Wherein R 1, R 2, R 3and R 4representative has at least 1 C atom and organic group that can be identical or different, A -represent univalent anion, A 2-represent dianion, A 3-represent trivalent negatively charged ion.
8. according to the purposes of claim 7, it is characterized in that organic group R 1, R 2, R 3and/or R 4in at least one be the saturated or unsaturated C of at least one straight chain, side chain, ring-type or aromatics 6-C 50alkyl or assorted alkyl.
9. according to the purposes of claim 7, it is characterized in that organic group R 1, R 2, R 3and/or R 4in at least one be saturated or unsaturated C 1-C 4alkyl.
10. purposes according to Claim 8, is characterized in that organic group R 1, R 2, R 3and/or R 4in at least one be saturated or unsaturated C 1-C 4alkyl.
11. dry mortar preparatons, described dry mortar preparaton comprises at least one tackiness agent and at least one mixture, and described mixture comprises at least one quaternary organic ammonium compounds and at least one water-soluble organic polymer and optional other additive or the inorganic carrier material for containing at least one quaternary organic ammonium compounds.
12. mortar or concrete, described mortar or concrete comprise at least one tackiness agent and at least one mixture, and described mixture comprises at least one quaternary organic ammonium compounds and at least one water-soluble organic polymer and optional other additive or the inorganic carrier material for containing at least one quaternary organic ammonium compounds.
13. according to the dry mortar preparaton of claim 11 or according to the mortar of claim 12 or concrete, it is characterized in that the content of quaternary organic ammonium compounds is at least 0.0001 % by weight based on dry mortar preparaton, mortar or concrete solid body.
14. according to the dry mortar preparaton of claim 11 or according to the mortar of claim 12 or concrete, it is characterized in that the content of quaternary organic ammonium compounds is maximum 5 % by weight based on dry mortar preparaton, mortar or concrete solid body.
15. according to the dry mortar preparaton of claim 11 or according to the mortar of claim 12 or concrete, it is characterized in that the content of quaternary organic ammonium compounds is at least 0.0001 % by weight and maximum 5 % by weight based on dry mortar preparaton, mortar or concrete solid body.
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